Vanadium oxide monolayer catalysts : The vapor-phase oxidation of methanol

The oxidation of methanol over vanadium oxide, unsupported and applied as a monolayer on γ-Al2O3, CeO2, TiO2, and ZrO2, was studied between 100 and 400 °C in a continuous-flow reactor. At temperatures from 150 to about 250 °C two main reactions take place, (a) dehydration of methanol to dimethyl ether and (b) partial oxidation to formaldehyde. A very slight direct oxidation to CO2 proceeds simultaneously. At higher temperatures two further reactions take place, i.e., (c) consecutive oxidation of the ether and/or formaldehyde to CO and (d) consecutive oxidation of CO to CO2. Selectivity to formaldehyde increased with decreasing reducibility of the catalyst, which in turn was a function of the catalyst-support interactions. Since the reducibility of V(V) has been shown to be related to the charge/radius ratio of the cation of the carrier, the selectivity to formaldehyde is also determined by this ratio

Atmospheric-pressure plasma-enhanced spatial atomic layer deposition of silicon nitride at low temperature

Atmospheric-pressure plasma-enhanced spatial atomic layer deposition (PE-spatial-ALD) of SiNx is demonstrated for the first time. Using bis(diethylamino)silane (BDEAS) and N2 plasma from a dielectric barrier discharge source, a process was developed at low deposition temperatures (≤ 250 °C). The effect of N2 plasma exposure time and overall cycle time on layer composition was investigated. In particular, the oxygen content was found to decrease with decreasing both above-mentioned parameters. As measured by depth profile X-ray photoelectron spectroscopy, 4.7 at.% was the lowest oxygen content obtained, whilst 13.7 at.% carbon was still present at a deposition temperature of 200 °C. At the same time, deposition rates up to 1.5 nm/min were obtained, approaching those of plasma enhanced chemical vapor deposition and thus opening new opportunities for high-throughput atomic-level processing of nitride materials

High‐throughput area‐selective spatial atomic layer deposition of SiO 2 with interleaved small molecule inhibitors and integrated back‐etch correction for low defectivity

A first‐of‐its‐kind area‐selective deposition process for SiO2 is developed consisting of film deposition with interleaved exposures to small molecule inhibitors (SMIs) and back‐etch correction steps, within the same spatial atomic layer deposition (ALD) tool. The synergy of these aspects results in selective SiO2 deposition up to ~23 nm with high selectivity and throughput, with SiO2 growth area and ZnO nongrowth area. The selectivity is corroborated by both X‐ray photoelectron spectroscopy (XPS) and low‐energy ion scattering spectroscopy (LEIS). The selectivity conferred by two different SMIs, ethylbutyric acid, and pivalic acid has been compared experimentally and theoretically. Density Functional Theory (DFT) calculations reveal that selective surface functionalization using both SMIs is predominantly controlled thermodynamically, while the better selectivity achieved when using trimethylacetic acid can be explained by its higher packing density compared to ethylbutyric acid. By employing the trimethylacetic acid as SMI on other starting surfaces (Ta2O5, ZrO2, etc.) and probing the selectivity, a broader use of carboxylic acid inhibitors for different substrates is demonstrated. It is believed that the current results highlight the subtleties in SMI properties such as size, geometry, and packing, as well as interleaved back‐etch steps, which are key in developing ever more effective strategies for highly selective deposition processes